Polymerization of olefines



Patented Oct. 25, 1932 UNITED STATES-PATENT ornca IBI'IZ nommr, OI BEES MU, IICHAEL OTTO, OI LUDWIGSEAI'EN-ON-TE'E-EHINE, AND

' WALTER S'IEGEIANN', OF uomm-on-m-anmn,

Io Drawing. Application filed November 3,

It has already been proposed to polymerize olefines with the aid of ,boron fluoride.

We have found that this reaction is greatly accelerated by being carried out in the presence of hydrogen halides or of substances furnishing hydro en halides. For example, an addition of hy rogenfluoride or of substances furnishing hydrogen fluoride yields d results. The presence of moisture t 'erefore 11! also has an accelerating effect, since it furnishes hydrogen fluoride by interaction with the boron fluoride present. Also hydrogen iodide, hydrogen bromide, hydrogen chloride or substances furnishing them under the con- 16. ditions of working as, for example, the halon compounds of aliphatic or aromatic i'ocarbons or such halogen compounds, 1n particular such of halogens or halogen halides in the Friedel- Crafts reaction, such as acid halogenidesan I the like have agood e'flect.

'exene and mixtures of these substances may be mentioned as examples of open chain or cyclic olefines coming into'question as initial materials according to the process of the present invention.

The polymerization products derived from the said olefines or mixtures of olefines correspend in their composition to the general formula C H and are usually more or less viscous oils.

The following examples will further illus trate the nature of the invention, but the invention is not limited thereto. The parts are by weight.

Example 1 100 parts of ethylene when treated with 10 parts of boron fluoride (absolutely dry) yield 10 parts of oil in 14 hours.

i 100 parts of moist ethylene when treated with 10 parts of boron fluoride yield 90 to 95 parts of oil in 8 to 12 hours.

100 parts of ethylene when treated with 10 parts of boron fluoride and 2 to 3 parts of hydrogen fluoride, all absolutely dry, yield 90 to 95 parts of oil in 3 to 4 hours.

50 The conditions of working as regards temorganic nature as splitofl".

Ethylene, propylene, butylene or cyclo-' a yield of 70 parts of oil is o 1999, !eria1 Io. 405,718}, and in Germany June 88, 1887.

perature and pressure are the same in all cases.

Ewample 2 3 parts of boron fluoride are added tolOO parts of dry propylene and are shaken therewith at room temperature for 15. hours; a yield of 30 parts oil is thus obtained. f

If in the process according to the fore oing" paragraph moist propylene is employe under the same conditions of working a yield of 70 to 7 parts of oil is obtained.

If 3 parts of boron fluoride and 1 part of I hydro n propy ene quantitative polymerization takes .place already in half an hour.

Ezvample 3 o'f'about 35 parts of oil is obtained.

fluoride be added to 100'pa'rts of If under the same conditions as those e'mployed in the process according to the foregoing paragraph moist butylene is employed tained already in 2 hours.

100 parts of butylene when treated together with 2 parts of boron fluoride and 1 part of a hydrogen fluoride yield 9ll'parts of oilin a quarter of an hour.

The products obtained according to Examples 2 and 3 irrespectively of whether they are prepared from moist or dry olefines do not difler very considerably from one another.

' Under reduced pressure of 10 mm mercury gauge per cent thereof boil from 100 to 160 0., per cent from 160 to 240 C. and 20 per cent above about 240 C.

Example 4 100 parts of dry cyclohexene (a cyclic olefine) are treated together with 6 parts of process according to the two foregoing paragraphs are subjected to steam distillation.

In the case of the process according to the first paragraph, about 10- arts of a residue are obtained consisting o a viscous oil. The constituent distilled over with the steam has a refraction index of 1.4581.

In the case of the product obtained according to the process described in the second paragraph, the residue consists of 15 parts of a highly viscous oil. The constituent volatilized with the steam has a refraction index of 1.4932.

By fractionation of the constituent volatilized with steam, it was found that in the case of the product obtained according to the process described in the first paragraph 75 per cent of cyclohexene are recovered unchanged and that the remaining ,15 per cent boil at a temperature of about 95 C. under a reduced pressure of 12 mm mercu auge. This constituent had a refraction 1n ex of 1.4932 and could be identified as cyclohexylcyclohexene (the dimer of cyclohexene). arts of this latter product were obtained mm the product obtained according to the process described in the foregoing paragraph.

Example 5 parts of ethylene when treated together with 10 parts of boron fluoride and 12 parts of hydrogen iodide under an initial pressure of 100 atmospheres yield 75 parts of oil in 10 hours.

Ema/mph 6 100 parts of ethylene are treated together wth 10 parts of boron fluoride and 5 parts of ethyl fluoride under an initial pressure of 130 atmospheres for 10 hours, 100 parts of oil being thus obtained.

EwmnpZe 7 presence of a vaporous hydrogen ha 'de.

2. In the polymerization of olefines of the general formula (C H with the aid of boron fluoride, the step of operating in the presence of vaporous hydrogen fluoride.

3. In the polymerization of olefines with the aid of boron fluoride, the step of operating in the presence of a hydrogen halide produced in the reaction itself.

4. In the polymerization of .olefines with the aid of boron fluoride, the step of operating in the presence .of hydrogen fluoride produced, at least in. part, by the reaction mamas ofdwater vapor on the aforesaid boron fluor1 e. t

5. A process for the polymerization of propylene, which 00mg lses shaking moist propylene together wit 7 boron fluoride.

6. A process for the polymerization of propylene, which comprises shaking about 100 parts of moist propylene with about 3 parts of boron fluoride at about room temperature.

7. In the polymerization of an olefine gaseous under normal conditions of temperature and pressure with the aid of boron fluoride, the step of operating in the pres ence of a vaporous hydrogen halide.

8. In the polymerization of an olefine gaseous under normal conditions of temperature and presure with the aid of boron fluoride, the ste of operatin in the presence of va orous hy rogen fluoride.

n testimony whereof we have hereunto set our hands.

FRITZ HOFMANN. MICHAEL OTTO. WALTER STEGEMANN. Q0 

